Chemistry on the inside: green chemistry in mesoporous materials

An overview of the rapidly expanding area of tailored mesoporous solids is presented. The synthesis of a wide range of the materials is covered, both inorganically and organically modified. Their applications, in particular those relating to green chemistry, are also highlighted. Finally, potential future directions for these materials are discussed

Catalytic performance of carbonaceous materials in the esterification of succinic acid

Mesoporous carbonaceous materials have outstanding potential in many different applications such as adsorption, medicine and catalysis. We have recently reported the synthesis of a new form of mesoporous carbon, named Starbon((R)), obtained after low temperature carbonization of expanded starch. Such starch-derived mesoporous materials have several tunable properties including surface energies (ranging from hydrophilic to hydrophobic surfaces), which can be easily controlled by the degree of carbonization (from 200 to 700 degrees C). Due to the diversity of surface functional groups, Starbons((R)) can be easily chemically modified. Treatment of Starbon((R)) materials with sulfuric acid gave a solid acid that has promising properties as heterogeneous catalyst. Comparative catalytic studies with some other similar commercial carbonaceous materials such as DARCO((R)) and NORIT (R), as well as phosphorous-containing microporous carbons, are reported. (c) 2008 Elsevier B.V. All rights reserved

Effect of spruce-derived phenolics extracted using microwave enhanced pyrolysis on the oxidative stability of biodiesel

An investigation has been carried out to characterize and evaluate phenolic compounds of bio-oils produced by the microwave enhanced pyrolysis of spruce woodchips (picea abies) for their potential application in stabilizing biodiesel from autoxidation. Four extracts were isolated from the bio-oil through multi-fractionation steps using a liquid-liquid extraction method: water-soluble, neutral, phenolic and organic acids extracts. The crude bio-oil and the isolated extracts were characterized by GC-MS, GC-FID, total phenols by Folin-Ciocalteu assay, ATR-IR and 13C NMR. The antioxidative effect of the crude bio-oil, its isolated extracts and two significant phenolic components (eugenol and catechol) of the crude bio-oil were also investigated using methyl linoleate as a biodiesel model by means of a high temperature (120°C) oxidation test. The results show that methyl linoleate induction time increased after blending small amounts (1.4-5.6% w/w) of either the crude bio-oil or the isolated extracts. However, the crude bio-oil showed higher induction times in comparison with its isolated extracts, which was significant because the crude bio-oil contained a lower concentration of phenolic species (23% w/w), especially in comparison to the phenolic concentration in the phenolic extract (49.6% w/w). Furthermore, catechol was found to be very effective and was similar to crude bio-oil in the inhibition of methyl linoleate autoxidation, unlike eugenol, which was less effective at equivalent molar concentrations. Also, the effect of catechol and the crude bio-oil on methyl linoleate induction time was approximately comparable with a commercial antioxidant (butylated hydroxytoluene) when treated at equivalent molar concentration of phenols

Synthesis of unsaturated polyester resins from various bio-derived platform molecules

Utilisation of bio-derived platform molecules in polymer synthesis has advantages which are, broadly, twofold; to digress from crude oil dependence of the polymer industry and secondly to reduce the environmental impact of the polymer synthesis through the inherent functionality of the bio-derived platform molecules. Bulk polymerisation of bio-derived unsaturated di-acids has been employed to produce unsaturated polyester (UPEs) which have been analysed by GPC, TGA, DSC and NMR spectroscopy, advancing on the analysis previously reported. UPEs from the diesters of itaconic, succinic, and fumaric acids were successfully synthesised with various diols and polyols to afford resins of MN 480-477,000 and Tg of -30.1 to -16.6 °C with solubilities differing based on starting monomers. This range of properties allows for many applications and importantly due to the surviving Michael acceptor moieties, solubility and cross-linking can be specifically tailored, post polymerisation, to the desired function. An improved synthesis of itaconate and succinate co-polymers, via the initial formation of an itaconate bis-diol, is also demonstrated for the first time, resulting in significantly improved itaconate incorporation

P-cymenesulphonyl chloride : A bio-based activating group and protecting group for greener organic synthesis

A bio-derived protecting/activating group has been synthesized by introducing a sulphonyl chloride group to the aromatic ring of p-cymene derived from citrus peel waste. The resulting p-cymenesulphonyl chloride was evaluated as an activating group by reacting with 1-octanol, 2-octanol, phenol and piperidine, and further reactions of the activated alcohols. The comparison to tosyl chloride demonstrates that the bio-based alternative can be effectively utilized as a direct replacement for the current fossil derived equivalent

Facile and rapid decarboxylation of glutamic acid to γ-aminobutyric acid via microwave-assisted reaction : towards valorisation of waste gluten

The growing trend towards the utilisation of biomass to produce fuels and chemicals has the potential to produce large quantities of protein-rich wastes that may be unsuitable for use as a feed. This protein waste could instead serve as a sustainable feedstock for the production of useful nitrogen-containing bio-based chemicals. We report herein the production of γ-aminobutyric acid from glutamic acid via a microwave-assisted decarboxylation reaction using isophorone as an inducer reagent. High yields of 63% can be achieved with only short reaction times (7 min) required. The influences of inducer loading, reaction time and hydrochloric acid concentration used for hydrolysis step of the work up were investigated at different scales. As a proof of concept, glutamic acid was facilely isolated from waste gluten, via microwave assisted hydrolysis, and subsequently decarboxylated with success. To the best of our knowledge this is the first organocatalytic route to γ-aminobutyric acid using glutamic acid as a reagent, and represents an alternative cleaner route to a valuable precursor for bio-based solvents, polymers and pharmaceuticals

Torrefied fuel pellets from solid waste of sugar industry

The preparation of fuel pellets from the filter cake waste from the sugar industry was studied. Pelletization by a hydraulic press at a pressure of 20 to 50 bar (2 to 5 MPa) was used to produce fuel pellets with a diameter of 1 cm and height of 1. 25 cm. Energy efficiency of the resulting pellets was improved by thermal treatment called “torrefaction”. During this process, the samples were heated to between 200 and 300°C for 0.5 to 2 h under a nitrogen atmosphere. The properties of fuel pellets including calorific value, bulk density, pellet density, proximate analysis, and compressive strength were characterized. The results demonstrated that the minimum pressure needed to produce the pellets without binder was 30 bar. The calorific value was between 13,954–14,468 kJ/ kg for the resulting fuel pellet, which was significantly higher than that of the unpelletized raw material (11,197 kJ/ kg). The fuel pellets had bulk density and pellet density of between 300–440 kg/m3 and 720–890 kg/m3, respectively. Increasing the time and temperature of torrefaction resulted in the lower yields of pellets. Fuel pellets maintain their shape and did not break under the applied torrefaction conditions. Torrefied pellets resulted in higher calorific value of 16,552–22,642 kJ/kg, higher carbon content, lower pellet and bulk densities compared to the fuel pellet without thermal treatment. The compressive strength of torrefied pellets decreased due to the delicate nature of the sample. The suggested conditions for optimal torrefied pellet in thermal and physical properties are 300°C and 1 h. The prepared fuel pellets showed comparable heating values to other fuels, and had properties in agreement with Thailand standards. Therefore, filter cake as a solid waste from production process of sugar has potential as raw material for the production of solid fuel pellets

Novel mesoporous carbon-silica composites from vinasse for the removal of dyes from aqueous silk dyeing wastes

Novel mesoporous carbon-silica composites were prepared from vinasse, a by-product from ethanol production, as the carbon source, and sodium silicate (Na2SiO3) and potassium silicate (K2SiO3) as low-cost silica source alternatives to tetraethyl orthosilicate (TEOS). The composites were characterized for their surface area and porous properties using nitrogen adsorption-desorption porosimetry. The composites possessed a high mesopore volume (45-77%) with moderate specific surface areas (343-656 m2/g) and pore size of 3.12-5.58 nm. The adsorption behaviour of carbon-silica composites for the removal of four silk dyes (Green 41, Blue 32, Dark red 34 and Dark gold brown 35) from aqueous solution was investigated and compared with a commercial activated carbon. The effects of adsorption time, dye concentration, pH and temperature were analyzed. The dye adsorption kinetics of all four dyes followed the pseudo-second order kinetic model, suggesting chemisorption as the dominant mechanism. Moreover, the intraparticle diffusion model showed that both internal diffusion and external diffusion were rate-limiting. The maximum adsorption capacities for all dyes were found at pH ~ 2. The equilibrium data for silk dyes adsorption were best described by the Langmuir equation, thus indicating monolayer adsorption. Thermodynamic parameters indicated that the dye adsorption was an endothermic process (ΔH > 0). The negative values of free energy (ΔG) confirmed that dye adsorption was spontaneous at the investigated temperatures (303-323 K). For all dyes, the maximum adsorption capacities of carbon-silica composites were comparable to the commercial activated carbon. The combination of vinasse with low-cost silica sources is a promising approach to produce inexpensive carbon-silica composites for application as adsorbents for dye removal from aqueous waste solutions generated during silk manufacture and dyeing

Subtle Microwave-Induced Overheating Effects in an Industrial Demethylation Reaction and Their Direct Use in the Development of an Innovative Microwave Reactor

A systematic study of the conventional and microwave (MW) kinetics of an industrially relevant demethylation reaction is presented. In using industrially relevant reaction conditions the dominant influence of the solvent on the MW energy dissipation is avoided. Below the boiling point, the effect of MWs on the activation energy Ea and k0 is found nonexistent. Interestingly, under reflux conditions, the microwave-heated (MWH) reaction displays very pronounced zero-order kinetics, displaying a much higher reaction rate than observed for the conventionally thermal-heated (CTH) reaction. This is related to a different gas product (methyl bromide, MeBr) removal mechanism, changing from classic nucleation into gaseous bubbles to a facilitated removal through escaping gases/vapors. Additionally, the use of MWs compensates better for the strong heat losses in this reaction, associated with the boiling of HBr/water and the loss of MeBr, than under CTH. Through modeling, MWH was shown to occur inhomogeneously around gas/liquid interfaces, resulting in localized overheating in the very near vicinity of the bubbles, overall increasing the average heating rate in the bubble vicinity vis-à-vis the bulk of the liquid. Based on these observations and findings, a novel continuous reactor concept is proposed in which the escaping MeBr and the generated HBr/water vapors are the main driving forces for circulation. This reactor concept is generic in that it offers a viable and low cost option for the use of very strong acids and the managed removal/quenching of gaseous byproducts

Work-hardening Photopolymer from Renewable Photoactive 3,3’-(2,5-Furandiyl)bisacrylic Acid

The design of a photopolymer around a renewable furan-derived chromophore is presented herein. An optimised semi-continuous oxidation method using MnO2 affords 2,5-diformylfuran from 5-(hydroxymethyl)furfural in gram quantities, allowing the subsequent synthesis of 3,3’-(2,5-furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. The photoactivity of the diester of this monomer is confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD-DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols are prepared via chemo- and enzyme-catalysed polycondensation. The latter enzyme-catalysed (Candida antarctica lipase B) method results in the highest Mn (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer's photoactivity and stereoisomerism. The photoreactive polyester is solvent cast into a film where subsequent initiator-free UV curing leads to an impressive increase in the material stiffness, with work-hardening characteristics observed during tensile strength testing